Silicone ester quaternary compounds

ABSTRACT

The present invention is directed to a novel dimethicone copolyol halo ester intermediate which conforms to the following structure; ##STR1## wherein R&#34; is --C(O)--CH 2  --Cl; 
     a is an integer from 0 to 200; 
     b is an integer from 0 to 200; 
     c is an integer from 1 to 200; 
     R 1  is selected from --(CH 2 ) n  CH 3  or phenyl; 
     n is an integer from 0 to 10; 
     R 2  is --(CH 2 ) 3  --(OCH 2  CH 2 )x--(OCH 2  CH(CH 3 ))y--(OCH 2  CH 2 )z--OH; 
     x, y and z are integers and are independently selected from 0 to 20, which is useful as an intermediate for reaction with amines to prepare silicone based quaternary compounds.

RELATED APPLICATION

This application is a continuation in part of copending application Ser.No. 07/674,410, filed Mar. 25, 1991, now U.S. Pat. No. 5,098,979.

BACKGROUND OF THE INVENTION

(1) Field of Invention

The present invention relates to a series of novel quaternary siliconepolymers, an intermediate useful in softening hair, and fiber andconditioning skin.

Since the compounds of the present invention are high molecular weightsilicone polymers, they have a high degree of oxidative stability, evenat elevated temperatures. In addition, these compounds are non volatileand unlike many other traditional fatty quaternary compounds are nonyellowing when applied to textile substrates and are non irritating toeyes and skin.

The compounds of the present invention are prepared by the reaction ofchloracetic acid with a pendant hydroxyl group which is present on asilicone polymer, followed by the reaction of the halo-ester with atertiary amine to give a quaternary compound. In a preferred embodimentthe hydroxy containing silicone polymer has been alkoxylated withethylene oxide, propylene oxide, or mixtures thereof. The ability toregulate both the type of alkylene oxide and amount of alkylene oxidepresent in the silicone polymer results in a series of products rangingin water/oil solubility. The technology used to produce the compounds ofthe present invention is very flexible and allows us to prepareperformance tailored molecules for specific applications.

(2) Object of the Invention

It is the object of the present invention to provide a series of novelquaternary silicone polymers, which are substantive to skin and hair.This substantivity results in superior softening, conditioning andantistatic properties. The compounds of the present invention contain afatty portion which is derived from a fatty amine. Incorporation of thistype of group into the silicone molecule results in increased solubilityin many organic solvents. This ability to marry fatty chemistry withsilicone chemistry results in unexpected solubilities and surface activeproperties. The compounds also contain varying amounts of ethylene oxideand propylene oxide in the molecule. This results in the ability to varywater solubility and introduce an inverse cloud point into the molecule.Inverse cloud point is well known to those skilled in the surfactantart. It is generally found in nonionic surface active agents. It is notfound in quaternary compounds. The inverse cloud point is thattemperature at which a soluble compound looses it's solubility in water.Inverse cloud point, also called high cloud point, is thought to beassociated with the ability of the alkyleneoxide chain to hydrogen bondwith the water.

It is another objective of the current invention to provide quaternarysilicone polymers which have very low irritation values when applied toskin and eyes. Irritation is a major problem with traditional fattycationic materials.

Still another object of the present invention is to provide a series ofquaternary silicone polymers which have differing solubilities in waterand organic solvents. This is achieved by selection of the hydroxysilicone polymer used as a raw material.

Application of the compounds of the invention can be from solvent,aqueous dispersion or solution, or applied neat in these process. It isanticipated that the effective conditioning concentration of thecompound of this invention ranges from 0.1% to 25% by weight.

The silicone polymers, suitable as raw materials, in a preferredembodiment, contain varying amounts of ethylene oxide, propylene oxideor mixtures thereof. The presence of the oxide in the silicone polymerresults in compounds with an inverse cloud point. Inverse cloud pointphenomenon are well known to those skilled in the art of nonionicsurface active agents. The inverse cloud point is defined as atemperature above which the polymer has minimal solubility in water. Ifheat is applied to an aqueous solution of the nonionic at the inversecloud point the material will become insoluble, and the solution willturn milky. It is at this point that the polymer has minimal watersolubility. Since the product is no longer in solution at above thistemperature, it is within this temperature range that the product hasmaximum substantivity to a fiber. The ability to use temperature todeposit a lubricant, antistat onto a fiber offers a great advantage incost effectiveness of fiber treatment, and results in less productusage.

(3) DESCRIPTION OF THE ARTS AND PRACTICES

Silicone oils (dimethylpolysiloxane) have been known to be active at thesurface of plastic, cellulosic and synthetic fibers as well as paper.Despite the fact that they are lubricants that are stable to oxidation,their high cost and lack of durability has made them cost prohibitive inmost application areas. Silicone oils need to be emulsified prior toapplication. This requires high pressure equipment, surface activeagents and generally results in a milky emulsion. Emulsions haveexperienced stability problems both in terms of freeze thaw instabilityand upon heating. This has resulted in minimal acceptance of them incommercial products.

The low efficiency of silicone oils is due to the fact that the oil isvery water insoluble. Emulsions are generally prepared which containsilicone dispersed in micelles. While this method of application iseasier for processing, much of the oil stays in the surfactant micelleand never gets deposited on the fiber. That which does deposit on thefiber surface remains there by hydrophobic binding, not ionic bonding.Since the polydimethylsiloxane is not ionically bonded the effect isvery transient. The product is removed with one washing.

Fatty quaternary compounds have been known as softerners for many years.They have a much lower molecular weight than the silicone basedcompounds of the present invention. For this reason, they are much moreirritating to skin and eyes than those materials based upon siliconepolymers.

Standard fatty quaternary compounds are prepared by quaternization of atertiary amine with such agents as benzyl chloride or di-methyl sulfateor di-ethyl sulfate or methyl cloride. These materials are relativelyinexpensive but offer several key disadvantages. These include yellowingof fabrics, a tendency to build-up upon repeated treatment, andvariability in hand (i.e. softness and feel). Standard softeners usedare selected from the following classes:

Class #1. Alkyl Imidazoline Quaternary Compounds made from thequaternization of an imidazoline made by reacting diethylenetriamine,and a high molecular weight fatty acid such as stearic acid. Thestandard quaternizating agents are di-ethyl sulfate, or methyl chloride,or di-methyl sulfate, or methyl chloride or benzyl chloride.

Class #2. Alkyl or dialkyl tertiary amines quaternized with benzylchloride or di-ethyl sulfate or methyl chloride or di-methyl sulfate.

Class #3. Quaternary compounds of ethoxylated, propoxylated ornonalkoxylated amido amines derived from the reaction of a highmolecular weight fatty acid like stearic acid and a polyamine likediethylene triamine. The standard quaternizating agents are di-ethylsulfate or di-methyl sulfate or methyl chloride or benzyl chloride.

Class #4. Amido amine salts derived from partially acid neutralizedamines.

It is known that under certain catalytic conditions, epichlorohydrinreacts with certain alcohols to give an intermediate which can be usedto react with tertiary amines to quaternary compounds. U.S. Pat. No.3,445,440 to Susi (May 1969) and U.S. Pat. No. 3,517,045 to Susi (June1970) teaches the use of chlorohydroxypropyl ether to alkylate specifictertiary amines which are the reaction product of a primary fatty amineand ethylene or propylene oxide. The compounds are used as antistaticagents in polymeric compositions such as polyolefin. The antistaticproperties of these compounds are achieved by the minimization of staticcharges on the polymer surface. These anti-static materials areincorporated into the polymer melt and are effective by virtue of theirinsolubility in the molten polymer. The quaternary compounds migrate tothe polymer surface and are effective antistatic agents.

U.S. Pat. No. 4,144,122 to Emanuelsson issued Mar. 13, 1979 teaches thattallow alcohol and certain other higher molecular weight non-guerbetalcohols and their alkoxylates can be reacted with epichlorohydrin, thensubsequently with tertiary amines to give compounds suitable for paperdebonding.

U.S. Pat. No. 4,215,064 to Lindemann et al issued Jul. 29, 1980 teachesthat phosphobetaines can be prepared by the reaction of a phosphate orphosphite salt with epichlorohydrin under aqueous conditions. U.S. Pat.No. 4,283,541 to O'Lenick, et al, issued Aug. 11, 1981 teaches theprocess for the preparation of the phosphobetaines described inLindemann (U.S. Pat. No. 4,215,064). None of these patents teach thecompounds of the present invention.

U.S. Pat. No. 4,800,077 issued Jan. 1989 to O'Lenick teaches guerbetalcohol quaternary compounds can be prepared by reacting epichlorohydrinwith guerbet alcohols then subsequently reacting the intermediate withamines.

None of the above incorporate silicone into the quaternary compound.Consequently, the unique softening and substantivity properties achievedusing the compounds of the present invention are not realized with theabove technologies.

THE INVENTION 1) Summary of the Invention

The present invention relates to a series of novel quaternary siliconepolymers. These polymers have a pendant quaternary nitrogen functionalgroup present. The polymers by virtue of the pendent group deposit onhair, skin and fiber surfaces forming effective nonvolatilenonirritating, surface modifying finishes. The compounds of the presentinvention are excellent conditioners, antistats and non-yellowing,softeners.

The compounds of this invention are represented by the followingformula;

    R--O--C(O)--CH.sub.2 --R'

wherein

R is ##STR2## a is an integer from 0 to 200; b is an integer from 0 to200;

c is an integer from 1 to 200;

R¹ is selected from --(CH₂)_(n) CH₃ or phenyl;

n is an integer from 0 to 10;

R² is --(CH₂)₃ --(OCH₂ CH₂)x--(OCH₂ CH(CH₃))y--(OCH₂ CH₂)z--OH;

x, y and z are integers and are independently selected from 0 to 20;

R' is selected from ##STR3## R³, R⁴, and R⁵ are each independently alkylhaving from 1 to 20 carbon atoms; ##STR4## R⁶ is alkyl having from 6 to20 carbon atoms; R⁷ and R⁸ are independently selected from methyl andethyl; or ##STR5## wherein R⁹ is alkyl having from 6 to 20 carbon atoms;

v is an integer from 1 to 5.

The products of the present invention are prepared by reaction of ahydroxyl containing silicone polymer with a halo acid, most commonlychloracetic acid resulting in a halo ester which in a subsequent step isreacted with an amine to give the desired quaternary compounds.

DIMETHICONE COPOLYOL HALO-ESTER INTERMEDIATE

The intermediate silicone copolyol halo-ester is an additional aspect ofthe present invention. It is useful as an intermediate in thepreparation of the compounds of the present invention. ##STR6## whereinR" is --C(O)--CH₂ --Cl; a is an integer from 0 to 200;

b is an integer from 0 to 200;

c is an integer from 1 to 200;

R¹ is selected from --(CH₂)_(n) CH₃ or phenyl;

n is an integer from 0 to 10;

R² is --(CH₂)₃ --(OCH₂ CH₂)x--(OCH₂ CH(CH₃))y--(OCH₂ CH₂)z--OH;

x, y and z are integers and are independently selected from 0 to 20.

The compounds of the related invention of which this is a continuationin part are based upon the reaction of epichlorohydrin with adimethicone copolyol. We have unecxpectantly found that theesterification reaction of the dimethicone copolyol is easier andresults in improved purity. The ester linkage also results in somewhatimproved solubility of the quat in polar solvents.

DIMETHICONE COPOLYOL REACTANTS

One method of preparing the reactive hydroxyl containing siliconepolymer is to react silanic hydrogen containing polymer with allylalcohol or allyl alcohol alkoxylate monomer. Procedures this reactionare well known to those skilled in the art. U.S. Pat. No. 4,083,856describe suitable processes.

EXAMPLES Vinyl Intermediate Compounds

Compounds of this class are prepared by alkoxylation of allyl alcoholusing methods well known to those skilled in the art. The following aresome of the many compounds which can be used to make the products ofthis invention.

    __________________________________________________________________________    CH.sub.2 ═CH--CH.sub.2 --O--(CH.sub.2 --CH.sub.2 --O)x--(CH.sub.2         --CH(CH.sub.3)--O)y--(CH.sub.2 --CH.sub.2 --O)z--H                                                       Molecular                                          Designation  x y        z  Weight                                             __________________________________________________________________________    A             3                                                                              0        0    189                                              B             9                                                                              27       3  2,178                                              C            11                                                                              3        0    718                                              D             0                                                                              0        0    57                                               E            20                                                                              20       20 2,940                                              F            20                                                                              0        0    880                                              G            10                                                                              10       10 1,470                                              __________________________________________________________________________

PREPARATION OF INTERMEDIATES

Silicone intermediates of the type used to make the compounds of thisinvention are well known to those skilled in the art. InternationalPublication (Silicone Alkylene Oxide Copolymers As Foam Control Agents)WO 86/0541 by Paul Austin Sep. 25, 1986) p. 16 (examples 1 to 6) is oneof many references which teaches how to make the followingintermediates.

HYDROSILATION OF INTERMEDIATES Silanic Hydrogen Containing Compounds

    ______________________________________                                         ##STR7##                                                                     Group Designations                                                                                         Average Equivalent                                      Austin    Group       Molecular                                                                             Molecular                                Example                                                                              Example   Designation Weight  Weight                                   ______________________________________                                        1      1         MD.sub.20 D*.sub.3.2 M                                                                    1,850   551                                      2      4         MD.sub.160 D*.sub.5 M                                                                     24,158  4,831                                    3      6         MD.sub.20 D*.sub.10 M                                                                     2,258   225                                      ______________________________________                                    

HYDROSILATION COMPOUNDS

The hydrosilation reaction used to make the compounds of this inventionare well known to those skilled in the art. Reference; InternationalPublication (Silicone Alkylene Oxide Copolymers As Foam Control Agents)WO 86/0541 by Paul Austin (Sep. 25, 1986) p.19.

EXAMPLE 4

To a 22 liter three necked round bottom flask fitted with a mechanicalagitator, thermometer with a Therm-o-watch temperature regulator,nitrogen sparge tube vented reflux condenser and heating mantle is added189.0 grams of Vinyl Intermediate Example #A. Next add 225 grams ofSilanic Hydrogen Containing Compound Example #3 and 3,000 grams oftoluene. Heat to 115 C. to remove azeotropically remove any water and200 ml of toluene. The temperature is reduced to 85 C. and 3.5 ml of 3%H₂ PtCl₆ in ethanol is added. Light to then excluded from the flask bycovering it with a black cloth. An exotherm is noted to about 95 C.,while the contents are stirred for about 2 hours. During this timesilanic hydrogen concentration drops to nil. Cool to 65 C. and slowlyadd 60 g of sodium bicarbonate. allow to mix overnight and filterthrough a 4 micron pad. Distill off any toluene at 100 C. and 1 torr.

EXAMPLE 5-10

The above procedure is repeated, only this time replacing both thesilanic hydrogen compound #3 with the specified number of grams of thespecified silanic hydrogen compound and the vinyl intermediate example Awith the specified number of grams of the specified vinyl intermediate.

    ______________________________________                                                             Silanic                                                          Vinyl Intermediate                                                                         Hydrogen Compound                                        Example   Example  Grams     Example                                                                              Grams                                     ______________________________________                                        4         A          189.0   1      551.0                                     5         B        2,178.0   2      4,831.0                                   6         C          718.0   3      225.0                                     7         D          57.0    1      551.0                                     8         E        2,940.0   2      4,831.0                                   9         F          880.0   3      225.0                                     10        G        1,470.0   1      551.0                                     ______________________________________                                    

PREPARATION OF THE SILICONE HYDROXYPROPYLETHER HALIDE Reaction Sequence##STR8##

The following examples further illustrate the objects and advantages ofthis invention, though it should be understood that the variousreactants and amounts thereof, reaction conditions, and other detailsare merely illustrative and should not be construed to unduly limit thisinvention.

General Procedure

Place the indicated amount of the dimethicone copolyol produced by theexample shown in a suitable vessel. Add the desired amount of catalystas shown under good agitation and a nitrogen sparge. The specifiedamount of monochloracetic acid is added. A molar excess of 0.1 to 0.5 ofchloracetic acid is added. The temperature is held between 160-200degrees C. for two to six hours. Reaction progress is monitored by acidvalue analysis and at the end of the reaction reaches theoretical forthe mole ratio used.

    ______________________________________                                                                 Grams of                                                             Grams of Catalyst                                             Dimethicone Copolyol                                                                            Chloroacetic      Stannous                                  Example                                                                              Example # Grams    Acid     SnO  Oxylate                               ______________________________________                                        11     4          740.0   94.0     4    0                                     12     5         7009.0   94.0     2    2                                     13     6          943.0   94.0     0    4                                     14     7          608.0   94.0     4    0                                     15     8         7771.0   94.0     2    2                                     16     9         1105.0   94.0     0    4                                     17     10        2021.0   94.0     4    0                                     ______________________________________                                    

QUATERNARY REACTION SEQUENCE

All amine reactants are commercially available from Tomah ProductsDivision of Exxon Chemicals Milton Wi. ##STR9## The following examplesfurther illustrate the objects and advantages of this invention, thoughit should be understood that the various reactants and amounts thereof,reaction conditions, and other details are merely illustrative andshould not be construed to unduly limit this invention.

AMINE REACTANT GROUP 1

The reactants are tertiary amines conforming to the following structure;

    ______________________________________                                         ##STR10##                                                                    Example Number R.sup.3   R.sup.4   R.sup.5                                    ______________________________________                                        18             C.sub.10 H.sub.21                                                                       CH.sub.3  CH.sub.3                                   19             C.sub.12 H.sub.25                                                                       CH.sub.3  CH.sub.3                                   20             C.sub.14 H.sub.29                                                                       CH.sub.3  CH.sub.3                                   21             C.sub.16 H.sub.33                                                                       CH.sub.3  CH.sub.3                                   22             C.sub.18 H.sub.37                                                                       CH.sub.3  CH.sub.3                                   23             C.sub.20 H.sub.41                                                                       CH.sub.3  CH.sub.3                                   24             C.sub.10 H.sub.21                                                                       C.sub.16 H.sub.33                                                                       CH.sub.3                                   25             C.sub.12 H.sub.25                                                                       C.sub.18 H.sub.37                                                                       CH.sub.3                                   26             C.sub.14 H.sub.29                                                                       C.sub.20 H.sub.41                                                                       CH.sub.3                                   27             C.sub.16 H.sub.33                                                                       C.sub.10 H.sub.21                                                                       CH.sub.3                                   28             C.sub.18 H.sub.37                                                                       C.sub.12 H.sub.25                                                                       CH.sub.3                                   29             C.sub.20 H.sub.41                                                                       C.sub.14 H.sub.29                                                                       CH.sub.3                                   30             C.sub.6 H.sub.13                                                                        C.sub.6 H.sub.13                                                                        C.sub.6 H.sub.13                           31             C.sub.2 H.sub.5                                                                         CH.sub.3  C.sub.2 H.sub.5                            32             C.sub.10 H.sub.21                                                                       C.sub.10 H.sub.21                                                                       C.sub.10 H.sub.21                          ______________________________________                                    

AMINE REACTANT GROUP 2

The reactants are amido tertiary amines conforming to the followingstructure;

    ______________________________________                                         ##STR11##                                                                    Example Number                                                                              R.sup.6   R.sup.7   R.sup.8                                     ______________________________________                                        33            C.sub.5 H.sub.11                                                                        CH.sub.3  CH.sub.3                                    34            C.sub.7 H.sub.15                                                                        CH.sub.3  CH.sub.3                                    35            C.sub.9 H.sub.19                                                                        CH.sub.3  CH.sub.3                                    36            C.sub.11 H.sub.23                                                                       CH.sub.3  CH.sub.3                                    37            C.sub.13 H.sub.27                                                                       CH.sub.3  CH.sub.3                                    38            C.sub.15 H.sub.31                                                                       CH.sub.3  CH.sub.3                                    39            C.sub.17 H.sub.35                                                                       CH.sub.3  CH.sub.3                                    40            C.sub.19 H.sub.39                                                                       CH.sub.3  CH.sub.3                                    41            C.sub.19 H.sub.39                                                                       CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.3                           42            C.sub.11 H.sub.23                                                                       CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.3                           43            C.sub.5 H.sub.11                                                                        CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.3                           44            C.sub.5 H.sub.11                                                                        CH.sub.3  CH.sub.3                                    45            C.sub.7 H.sub.15                                                                        CH.sub.3  CH.sub.3                                    46            C.sub.9 H.sub.19                                                                        CH.sub.3  CH.sub.3                                    47            C.sub.11 H.sub.23                                                                       CH.sub.3  CH.sub.3                                    48            C.sub.13 H.sub.27                                                                       CH.sub.3  CH.sub.3                                    49            C.sub.15 H.sub.31                                                                       CH.sub.3  CH.sub.3                                    50            C.sub.17 H.sub.35                                                                       CH.sub.3  CH.sub.3                                    51            C.sub.19 H.sub.39                                                                       CH.sub.3  CH.sub.3                                    ______________________________________                                    

AMINE REACTANT GROUP 3

The reactants are imidazoline compounds conforming to the followingstructure;

    ______________________________________                                         ##STR12##                                                                    Example Number         R.sup.9                                                ______________________________________                                        52                     C.sub.5 H.sub.11                                       53                     C.sub.7 H.sub.15                                       54                     C.sub.9 H.sub.19                                       55                     C.sub.11 H.sub.23                                      56                     C.sub.13 H.sub.27                                      57                     C.sub.15 H.sub.31                                      58                     C.sub.17 H.sub.35                                      59                     C.sub.19 H.sub.39                                      ______________________________________                                    

GENERAL REACTION PROCEDURE

The products of the present invention are generally prepared in aqueoussolution or dispersion. The preferred concentration is about 50% solids.Additionally, alcohols such as methanol, ethanol, isopropanol, glycolssuch as ethylene glycol, propylene glycol, polypropylene glycol,polyethylenegylcol, hexylene glycol, and cyclomethicone can be added toimprove clarity if desired.

To a suitable flask, equipped with a thermometer and agitator is addedthe specified amount of water. Next add the specified amount of the typeof silicone reactant. Heat to 50 C. Next add the specified amount of thespecified amine under good agitation. THe reaction mass is heated to85-95 C. and held from between 5 and 15 hours. The reaction progress ismonitored by % inorganic chloride, which approaches 98% of theoretical.

    ______________________________________                                        Amine Reactants  Silicone Reactants                                                                           Water                                         Example                                                                              Example  Grams    Example Grams  Grams                                 ______________________________________                                        60     18       185.0    11        834.0                                                                              1,019.0                               61     19       201.0    12      7,103.0                                                                              7,304.0                               62     20       227.0    13      1,037.0                                                                              1,264.0                               63     21       253.0    14        702.0                                                                                955.0                               64     22       279.0    15      7,865.0                                                                              8,144.0                               65     23       305.0    16      1,119.0                                                                              1,424.0                               66     24       364.0    17      3,115.0                                                                              3,479.0                               67     25       406.0    11        834.0                                                                              1,240.0                               68     26       458.0    12      7,103.0                                                                              8,801.0                               69     27       364.0    13      1,037.0                                                                              1,401.0                               70     28       406.0    14        702.0                                                                              1,108.0                               71     29       458.0    15      7,865.0                                                                              8,323.0                               72     30       251.0    16      1,119.0                                                                              1,370.0                               73     31        70.0    17      3,155.0                                                                              3,225.0                               74     32       437.0    11        834.0                                                                              1,271.0                               75     33       199.0    12      7,103.0                                                                              7,302.0                               76     34       227.0    13      1,037.0                                                                              1,264.0                               77     35       255.0    14        702.0                                                                                957.0                               78     36       283.0    15      7,865.0                                                                              8,148.0                               79     37       311.0    16      1,119.0                                                                              1,430.0                               80     38       339.0    17      3,155.0                                                                              3,494.0                               81     39       367.0    11        834.0                                                                              1,201.0                               82     40       395.0    12      7,103.0                                                                              7,498.0                               83     41       337.0    13      1,037.0                                                                              1,374.0                               84     42       311.0    14         702.0                                                                             1,013.0                               85     43       227.0    15      7,865.0                                                                              9,096.0                               86     44       640.0    16      1,119.0                                                                              1,831.0                               87     45       4,928.0  17      3,155.0                                                                              8,083.0                               88     46       300.0    11        834.0                                                                              1,134.0                               89     47       328.0    12      7,103.0                                                                              7,431.0                               90     48       1,782.0  13      1,037.0                                                                              2,819.0                               91     49       1,370.0  14        702.0                                                                              2,072.0                               92     50       1,103.0  15      7,865.0                                                                              8,968.0                               93     51       1,131.0  16      1,119.0                                                                              2,250.0                               94     52       184.0    17      3,155.0                                                                              3,339.0                               95     53       212.0    11        834.0                                                                              1,046.0                               96     54       240.0    12      7,103.0                                                                              7,343.0                               97     55       268.0    13      1,037.0                                                                              1,305.0                               98     56       296.0    14        702.0                                                                                998.0                               99     57       324.0    15      7,865.0                                                                              8,189.0                               100    58       352.0    16      1,119.0                                                                              1,471.0                               101    59       380.0    17      3,155.0                                                                              3,535.0                               ______________________________________                                    

APPLICATIONS EVALUATION Applications of the Compounds of The Invention

Compounds of this invention were compared to standard compoundscommercially available using AATCC Test Method 117-1979. The colorfastness heat test uses a 400 F. (205 F.) hot iron which is applied for60 and 180 seconds. The color is rated on a 1-5 basis for yellowness, (5being the most yellow).

    ______________________________________                                        Compound          CAS Number Yellowness                                       ______________________________________                                        Stearyl Imidazoline Quat                                                                        68122-86-1 4                                                (Alkaquat ST)                                                                 Distearyl Quat    61789-81-9 4                                                Tallow Amido Quat 65098-88-6 5                                                (Alkaquat DAET-90)                                                            Stearyl Amido Propyl Salt                                                                       68308-45-2 4                                                Example 63                   1                                                Example 92                   2                                                ______________________________________                                    

WET COMB OUT TEST

A laboratory test is conducted to screen the wet comb properties of arepresentative member of the family of novel compounds. Hair swatchesare purchased from a supply of human hair from the same head. Each testswatch contains 7 grams of hair and is 11 inches in length. The hair istied tightly 1 inch from one end with string. THe swatch is pre-cleanedwith a 3% solution of ammonium lauryl sulfate. Subsequently, the swatchis washed under running tap water. The hair is then squeezed out andwhile still damp dipped into a 200 ml solution of 0.2% activequaternary. Another rinse is made, then the swatch is blotted dry. Theswatch is then treated by holding the hair swatch, combing the hair asrapidly as possible while alternating the side of the swatch combed. Thetime needed to get one smooth free stroke without tangling is recorded.Typical results for the standard quaternary compounds used in hairconditioning (stearyldimethylbenzyl ammonium chloride) range from 12-14seconds.

    ______________________________________                                        Rinse Conditioner (Wet Comb Out Test)                                         Product          Time in Seconds                                              ______________________________________                                        Product Example 60                                                                             11                                                           Product Example 92                                                                             13                                                           Stearyldimethylbenzyl                                                                          12                                                           ammonium chloride                                                             ______________________________________                                    

As can be seen, the compounds of the invention give significantconditioning properties to hair, and coupled with their mild nature withregard to skin and eyes, makes it a prime candidate for cosmeticapplications.

I claim:
 1. A dimethicone copolyol halo ester intermediate whichconforms to the following structure; ##STR13## wherein; R" is--C(O)--CH₂ --Cl;a is an integer from 0 to 200; b is an integer from 0to 200; c is an integer from 1 to 200; R¹ is --(CH₂)_(n) CH₃ or phenyl;n is an integer from 0 to 10; R² is --(CH₂)₃ --(OCH₂ CH₂)x--(OCH₂CH(CH₃))y--(OCH₂ CH₂)z--OH; x, y and z are integers which independentlyrange from 0 to
 20. 2. A compound of claim 1 wherein x is 3, y is 0, andz is
 0. 3. A compound of claim 1 wherein x is 9, y is 27, and z is
 3. 4.A compound of claim 1 wherein x is 11, y is 3, and z is
 0. 5. A compoundof claim 1 wherein x is 0, y is 0, and z is
 0. 6. A compound of claim 1wherein x is 20, y is 20, and z is
 20. 7. A compound of claim 1 whereinx is 20, y is 0, and z is
 0. 8. A compound of claim 1 wherein x is 10, yis 10, and z is 10.